Low-viscosity opacifiers without anionic surface-active agents

ABSTRACT

An emulsifier mixture for use in a wax-based opacifier composition is comprised of: (a) an alkyl and/or alkenyl oligoglycoside; (b) a fatty acid partial glyceride and optionally (c) at least one amphoteric surfactant, with the proviso that the ratio by weight of (a) and optionally (c) to (b) is between 6:1 and 3:1 and wherein the composition is free from anionic surfactants.

BACKGROUND OF THE INVENTION

This invention relates to opacifiers containing waxes, an emulsifiermixture of alkyl and/or alkenyl oligoglycosides, fatty acid partialglycerides and optionally amphoteric surfactants in a certain ratio byweight, but no anionic surfactants, and to their use as opacifiers.

In the formulation of a number of surface-active household products,such as dishwashing detergents for example, or cosmetic preparations,such as hair shampoos for example, particular importance is attributedto the products being clear and not clouding, even in storage. In othercases, cloudy products with a shimmering effect known as pearlescenceare required for the same purpose. A third group of products is madewith a non-shimmering opaque whiteness using so-called opacifiers.

Opacifiers are fine-particle dispersions of polymers or solids which,apart from water and/or a polyol (for example glycerol), largely containonly a wax and a suitable emulsifier. Known opacifiers are mainly basedon copolymers based on acrylic or methacrylic acid and styrene and arenot biodegradable. German patent DE 19511572 C2 describes low-viscosityopacifier concentrates based on waxes, sugar surfactants and partialglycerides. Although these concentrates are readily biodegradable, theyhave high viscosities and are in need of improvement so far as theirparticle fineness is concerned.

Accordingly, the problem addressed by the invention was to provideopacifier preparations or concentrates based on waxes which would behighly concentrated but which would have distinctly reduced meanparticle sizes and lower viscosities by comparison with the prior artand would be biodegradable. In addition, the preparations according tothe invention would produce more intense whiteness, but no pearlescence,in aqueous surfactant solutions and, by virtue of their particle size,would be sufficiently stable in storage, even at elevated temperatures.Also, the addition of amphoteric surfactants would have no effect on thestability of such preparations.

DESCRIPTION OF THE INVENTION

The present invention relates to wax-based opacifier preparations whichare characterized in that they contain an emulsifier mixture of

-   (a) at least one alkyl and/or alkenyl oligoglycoside,-   (b) at least one fatty acid partial glyceride and optionally-   (c) at least one amphoteric surfactant,    with the proviso that the ratio by weight of (a) and optionally (c)    to (b) is between 6:1 and 3:1, preferably between 3.5:1 and 5:1 and    more particularly between 4:1 and 4.7:1 and the preparations are    free from anionic surfactants. In one particular embodiment of the    invention, the ratio by weight of components (a) and optionally (c)    to component (b) is between 5:1 and 1.5:1 and more particularly    between 3:1 and 2:1.

It has surprisingly been found that mixtures based on waxes with alkyloligoglycosides and partial glycerides in a selected ratio by weightgive products which have a particularly small mean particle sizes bycomparison with the prior art. Accordingly, the required white opaqueeffect is also intensified by these particularly fine-particlepreparations and no pearlescence is formed. In addition, these productshave particularly low viscosities, are biodegradable, show good flow andpumping properties and are sufficiently stable in storage. The productsretain their stability and favorable properties in the presence ofamphoteric surfactants, such as betaines for example. These advantageousproperties can only be achieved for opacifier systems free from anionicsurfactants.

Alkyl and/or Alkenyl Oligoglycosides

Alkyl and/or alkenyl oligoglycosides are known nonionic surfactantswhich correspond to formula (I):R¹O-[G]_(p)  (I)in which R¹ is an alkyl and/or alkenyl group containing 4 to 22 carbonatoms, G is a sugar unit containing 5 or 6 carbon atoms and p is anumber of 1 to 10. They may be obtained by the relevant methods ofpreparative organic chemistry. The overviews presented by Bierman et al.in Starch/Stärke 45, 281 (1993), by B. Salka in Cosm. Toil. 108, 89(1993) and by J. Kahre in SÖFW-Journal No. 8, 598 (1995) are cited asrepresentative of the extensive literature available on this subject.

The alkyl and/or alkenyl oligoglycosides may be derived from aldoses orketoses containing 5 or 6 carbon atoms, preferably glucose. Accordingly,the preferred alkyl and/or alkenyl oligoglycosides are alkyl and/oralkenyl oligoglucosides. The index p in general formula (I) indicatesthe degree of oligomerization (DP), i.e. the distribution of mono-andoligoglycosides, and is a number of 1 to 10. Whereas p in a givencompound must always be an integer and, above all, may assume a value of1 to 6, the value p for a certain alkyl oligoglycoside is ananalytically determined calculated quantity which is generally a brokennumber. Alkyl and/or alkenyl oligoglycosides having an average degree ofoligomerization p of 1.1 to 3.0 are preferably used. Alkyl and/oralkenyl oligoglycosides having a degree of oligomerization of less than1.7 and, more particularly, between 1.2 and 1.4 are preferred from theapplicational point of view. The alkyl or alkenyl radical R¹ may bederived from primary alcohols containing 4 to 11 and preferably 8 to 10carbon atoms. Typical examples are butanol, caproic alcohol, caprylicalcohol, capric alcohol and undecyl alcohol and the technical mixturesthereof obtained, for example, in the hydrogenation of technical fattyacid methyl esters or in the hydrogenation of aldehydes from Roelen'soxosynthesis. Alkyl oligoglucosides having a chain length of C₈ to C₁₀(DP=1 to 3), which are obtained as first runnings in the separation oftechnical C₈₋₁₈ coconut oil fatty alcohol by distillation and which maycontain less than 6% by weight of C₁₂ alcohol as an impurity, and alsoalkyl oligoglucosides based on technical C_(9/11) oxoalcohols (DP=1 to3) are preferred. In addition, the alkyl or alkenyl radical R¹ may alsobe derived from primary alcohols containing 12 to 22 and preferably 12to 14 carbon atoms. Typical examples are lauryl alcohol, myristylalcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearylalcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachylalcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidylalcohol and technical mixtures thereof which may be obtained asdescribed above. Alkyl oligoglucosides based on hydrogenated C_(12/14)coconut oil fatty alcohol having a DP of 1 to 3 are preferred.

The preparations according to the invention may contain the alkyl and/oralkenyl oligoglycosides in quantities of 0.1 to 20, preferably 5 to 18and more particularly 8 to 13% by weight, based on the finalcomposition.

Fatty Acid Partial Glycerides

Fatty acid partial glycerides, i.e. monoglycerides, diglycerides andtechnical mixtures thereof may still contain small quantities of di- andtriglycerides from their production. The partial glycerides preferablycorrespond to formula (II):

in which R²CO is a linear or branched, saturated and/or unsaturated acylgroup containing 6 to 22 and preferably 12 to 18 carbon atoms, R³ and R⁴independently of one another have the same meaning as R²CO or representOH and the sum (m+n+p) is 0 or a number of 1 to 100 and preferably 5 to25, with the proviso that at least one of the two substituents R³ and R⁴represents OH. Typical examples are mono- and/or diglycerides based oncaproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauricacid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleicacid, stearic acid, isostearic acid, oleic acid, elaidic acid,petroselic acid, linoleic acid, linolenic acid, elaeostearic acid,arachic acid, gadoleic acid, behenic acid and erucic acid and technicalmixtures thereof. Technical lauric acid glycerides, palmitic acidglycerides, stearic acid glycerides, isostearic acid glycerides, oleicacid glycerides, behenic acid glycerides and/or erucic acid glycerideswhich have a monoglyceride content of 50 to 95% by weight and preferably60 to 90% by weight are preferably used. Relatively long-chain partialglycerides, for example based on oleic acid or stearic acid, especiallymixtures of glycerides based on saturated and unsaturated fatty acids,are particularly suitable.

The preparations according to the invention may contain the fatty acidpartial glycerides in quantities of 0.1 to 5, preferably 1 to 3.5 andmore particularly 1.2 to 2.4% by weight, based on the final composition.

Amphoteric Surfactants

The preparations according to the invention may optionally containamphoteric surfactants such as, for example, alkyl betaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betainesand sulfobetaines. Betaines are preferably used. Betaines are knownsurfactants which are mainly produced by carboxyalkylation, preferablycarboxymethylation, of aminic compounds. The starting materials arepreferably condensed with halocarboxylic acids or salts thereof, moreparticularly with sodium chloroacetate, 1 mol of salt being formed permol of betaine. The addition of unsaturated carboxylic acids, forexample acrylic acid, is also possible. Particulars of the nomenclatureand, in particular, the distinction between betaines and “genuine”amphoteric surfactants can be found in the article by U. Ploog inSeifen-Öle-Fette-Wachse, 198, 373 (1982). Other reviews of this subjecthave been published, for example, by A. O'Lenick et al. in HAPPI, Nov.70 (1986), by S. Holzman et al. in Tens. Surf. Det. 23, 309 (1986), byR. Bibo et al. in Soap Cosm. Chem. Spec., Apr. 46 (1990) and by P. Elliset al. in Euro Cosm. 1, 14 (1994). Examples of suitable betaines are thecarboxyalkylation products of secondary and, in particular, tertiaryamines corresponding to formula (III):

in which R⁵ stands for alkyl and/or alkenyl groups containing 6 to 22carbon atoms, R⁶ stands for hydrogen or alkyl groups containing 1 to 4carbon atoms, R⁷ stands for alkyl groups containing 1 to 4 carbon atoms,n is a number of 1 to 6 and X is an alkali metal and/or alkaline earthmetal or ammonium. Typical examples are the carboxymethylation productsof hexyl methyl amine, hexyl dimethyl amine, octyl dimethyl amine, decyldimethyl amine, dodecyl methyl amine, dodecyl dimethyl amine, dodecylethyl methyl amine, C_(12/14) cocoalkyl dimethyl amine, myristyldimethyl amine, cetyl dimethyl amine, stearyl dimethyl amine, stearylethyl methyl amine, oleyl dimethyl amine, C_(16/18) tallow alkyldimethyl amine and technical mixtures thereof.

Other suitable betaines are carboxyalkylation products of amido-aminescorresponding to formula (IV):

in which R⁸CO is an aliphatic acyl group containing 6 to 22 carbon atomsand 0 or 1 to 3 double bonds, m is a number of 1 to 3 and R⁶, R⁷, n andX are as defined above. Typical examples are reaction products of fattyacids containing 6 to 22 carbon atoms, namely caproic acid, caprylicacid, capric acid, lauric acid, myristic acid, palmitic acid,palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidicacid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid,arachic acid, gadoleic acid, behenic acid and erucic acid and technicalmixtures thereof, with N,N-dimethyl aminoethyl amine, N,N-dimethylaminopropyl amine, N,N-diethyl aminoethyl amine and N,N-diethylaminopropyl amine which are condensed with sodium chloroacetate. It ispreferred to use a condensation product of C_(8/18) cocofattyacid-N,N-dimethyl aminopropyl amide with sodium chloroacetate.

Other suitable starting materials for the betaines to be used inaccordance with the invention are imidazolines corresponding to formula(V):

in which R⁵ is an alkyl group containing 5 to 21 carbon atoms, R⁶ is ahydroxyl group, an OCOR⁵ or NHCOR⁵ group and m=2 or 3. Imidazolines arealso known compounds which may be obtained, for example, by cyclizingcondensation of 1 or 2 mol of fatty acid with polyfunctional amines, forexample aminoethyl ethanolamine (AEEA) or diethylene triamine. Thecorresponding carboxyalkylation products are mixtures of differentopen-chain betaines. Typical examples are condensation products of theabove-mentioned fatty acids with AEEA, preferably imidazolines based onlauric acid or—again—C_(12/14) cocofatty acid which are subsequentlybetainized with sodium chloroacetate.

The preparations according to the invention may contain the amphotericsurfactants in quantities of 0 to 10, preferablyh 1 to 5 and moreparticularly 2 to 4% by weight, based on the final composition.

Waxes

Basically, the choice of the waxes is not critical. Typical examples arealkylene glycol fatty acid esters, wax esters, hydrogenatedtriglycerides, saturated fatty alcohols containing 16 to 18 carbonatoms, ethylene oxide adducts with C₁₆₋₁₈ fatty acids and/or paraffinwaxes.

Alkylene Glycol Fatty Acid Esters

In another preferred embodiment of the invention, the waxes used arealkylene glycol fatty acid esters corresponding to formula (VI):R⁹CO—O-[A]-O—R¹⁰  (VI)in which R⁹CO is an aliphatic acyl group containing 6 to 22 carbon atomsand 0 and/or 1, 2 or 3 double bonds, R¹⁰ has the same meaning as R⁹CO oris a hydroxyl group and A is a linear or branched, optionallyhydroxysubstituted alkylene group containing 2 to 5 carbon atoms.

These waxes are preferably esters of ethylene glycol or propylene glycolwith caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid,lauric acid, isotridecanoic acid, myristic acid, palmitic acid,palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidicacid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid,arachic acid, gadoleic acid, behenic acid and erucic acid and technicalmixtures thereof. The use of ethylene glycol distearate is particularlypreferred.

The preparations according to the invention may contain the waxes,preferably alkylene glycol fatty acid esters, in quantities of 10 to 35,preferably 12 to 28 and more particularly 15 to 25% by weight, based onthe final composition.

Commercial Applications

The opacifier preparations according to the invention have a solidscontent of preferably 20 to 45, more preferably 30 to 41 and mostpreferably 35 to 37% by weight, based on the final composition.Accordingly, the present invention also relates to their use asopacifiers, preferably in cosmetic preparations.

They are distinguished by low viscosities, preferably in the range from2,000 to 6,000 mPas and more particularly in the range from 2,500 to5,000 mPas (Brookfield: 23° C., spindle 5, 10 r.p.m.), by good flow andpumping properties and by particular particle fineness of the crystalsin the dispersion. The particular particle fineness is produced by aparticle size distribution where at least 85, preferably 90, morepreferably 95 and most preferably 99.9% of the particles have a diameterof <15 μm. The mean particle diameter is preferably <15, more preferably<10 and most preferably <7 μm.

Another advantage of the opacifier preparations according to theinvention is their high stability to sedimentation in the event ofprolonged storage. When used in quantities of 0.1 to 12, preferably 0.5to 6 and more particularly 1 to 3.5% by weight in aqueous surface-activecompositions, such as manual detergents for example, or in cosmeticand/or pharmaceutical preparations, such as for example hair shampoos,hair lotions, foam baths, shower baths, oral and dental care products,creams, gels, lotions, aqueous/alcoholic solutions, emulsions and thelike, the opacifier preparations according to the invention produce apermanent, uniform and—compared with the prior art—particularlyintensive white opaqueness without any pearlescence.

The choice of the surfactants in aqueous solutions of which thepreparations according to the invention produce a white opaqueness isvery important because the addition of anionic surfactants produces adistinct increase in viscosity and the required particle fineness andhence the particularly intensive white opaqueness fail to appear.Instead pearlescence is generally produced because relatively largeparticles are also present through the use of anionic surfactants.Accordingly, the opacifiers can only be used in aqueous solutions ofnonionic and/or amphoteric or zwitterionic surfactants. They arepreferably used in aqueous solutions containing amphoteric orzwitterionic surfactants.

The surfactant mixtures according to the invention may additionallycontain other surfactants, oil components, emulsifiers, pearlizingwaxes, consistency factors, thickeners, superfatting agents,stabilizers, polymers, silicone compounds, fats, waxes, lecithins,phospholipids, biogenic agents, UV protection factors, antioxidants,deodorants, antiperspirants, antidandruff agents, film formers, swellingagents, insect repellents, self-tanning agents, tyrosine inhibitors(depigmenting agents), hydrotropes, solubilizers, preservatives, perfumeoils, dyes and the like as further auxiliaries and additives.

Surfactants

Nonionic and/or cationic surfactants may be present as surfactants.Typical examples of nonionic surfactants are fatty alcohol polyglycolethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters,fatty acid amide polyglycol ethers, fatty amine polyglycol ethers,alkoxylated triglycerides, mixed ethers and mixed formals, optionallypartly oxidized glucuronic acid derivatives, fatty acid-N-alkylglucamides, protein hydrolyzates (particularly wheat-based vegetableproducts), polyol fatty acid esters, sugar esters, sorbitan esters,polysorbates and amine oxides. If the nonionic surfactants containpolyglycol ether chains, they may have a conventional homologdistribution, although they preferably have a narrow-range homologdistribution. Typical examples of cationic surfactants are quaternaryammonium compounds, for example dimethyl distearyl ammonium chloride,and esterquats, more particularly quaternized fatty acid trialkanolamineester salts. The surfactants mentioned are all known compounds.Information on their structure and production can be found in relevantsynoptic works, cf. for example J. Falbe (ed.), “Surfactants in ConsumerProducts”, Springer Verlag, Berlin, 1987, pages 54 to 124 or J. Falbe(ed.), “Katalysatoren, Tenside und Mineralöladditive (Catalysts,Surfactants and Mineral Oil Additives)”, Thieme Verlag, Stuttgart, 1978,pages 123–217.

Oil Components

Suitable oil components are, for example, Guerbet alcohols based onfatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms,esters of linear C₆₋₂₂ fatty acids with linear or branched C₆₋₂₂ fattyalcohols or esters of branched C₆₋₁₃ carboxylic acids with linear orbranched C₆₋₂₂ fatty alcohols such as, for example, myristyl myristate,myristyl palmitate, myristyl stearate, myristyl isostearate, myristyloleate, myristyl behenate, myristyl erucate, cetyl myristate, cetylpalmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetylbehenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearylstearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearylerucate, isostearyl myristate, isostearyl palmitate, isostearylstearate, isostearyl isostearate, isostearyl oleate, isostearylbehenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleylstearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleylerucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenylisostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucylmyristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyloleate, erucyl behenate and erucyl erucate. Also suitable are esters oflinear C₆₋₂₂ fatty acids with branched alcohols, more particularly2-ethyl hexanol, esters of C₁₈₋₃₈ alkyl hydroxycarboxylic acids withlinear or branched C₆₋₂₂ fatty alcohols (cf. DE 19756377 A1), moreespecially Dioctyl Malate, esters of linear and/or branched fatty acidswith polyhydric alcohols (for example propylene glycol, dimer diol ortrimer triol) and/or Guerbet alcohols, triglycerides based on C₆₋₁₀fatty acids, liquid mono-/di-/triglyceride mixtures based on C₆₋₁₈ fattyacids (cf. EP 97/00434), esters of C₆₋₂₂ fatty alcohols and/or Guerbetalcohols with aromatic carboxylic acids, more particularly benzoic acid,esters of C₆₋₂₂ dicarboxylic acids with linear or branched alcoholscontaining 1 to 22 carbon atoms or polyols containing 2 to 10 carbonatoms and 2 to 6 hydroxyl groups, vegetable oils, branched primaryalcohols, substituted cyclohexanes, linear and branched C₆₋₂₂ fattyalcohol carbonates, for example Dicaprylyl Carbonate (Cetiol® CC),Guerbet carbonates based on C₆₋₁₈ and preferaly C₈₋₁₀ fatty alcohols,esters of benzoic acid with linear and/or branched C₆₋₂₂ alcohols (forexample Finsolv® TN), linear or branched, symmetrical or nonsymmetricaldialkyl ethers containing 6 to 22 carbon atoms per alkyl group, forexample Dicaprylyl Ether (Cetiol® OE), ring opening products ofepoxidized fatty acid esters with polyols, silicone oils(cyclomethicone, silicon methicones) and/or aliphatic or naphthenichydrocarbons, for example squalane, squalene or dialkyl cyclohexanes.

Emulsifiers

Suitable emulsifiers are, for example, nonionic surfactants from atleast one of the following groups:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0        to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols,        C₁₂₋₂₂ fatty acids and alkyl phenols containing 8 to 15 carbon        atoms in the alkyl group and alkylamines containing 8 to 22        carbon atoms in the alkyl group;    -   alkyl and/or alkenyl oligoglycosides containing 8 to 22 carbon        atoms in the alk(en)yl group and ethoxylated analogs thereof;    -   products of the addition of 1 to 15 mol ethylene oxide onto        castor oil and/or hydrogenated castor oil;    -   products of the addition of 15 to 60 mol ethylene oxide onto        castor oil and/or hydrogenated castor oil;    -   partial esters of sorbitan with unsaturated, linear or        saturated, branched fatty acids containing 12 to 22 carbon atoms        and/or hydroxycarboxylic acids containing 3 to 18 carbon atoms        and addition products thereof with 1 to 30 mol ethylene oxide;    -   partial esters of polyglycerol (average degree of        self-condensation 2 to 8), trimethylolpropane, pentaerythritol,        sugar alcohols (for example sorbitol), alkyl glucosides (for        example methyl glucoside, butyl glucoside, lauryl glucoside) and        polyglucosides (for example cellulose) with saturated and/or        unsaturated, linear or branched fatty acids containing 12 to 22        carbon atoms and/or hydroxycarboxylic acids containing 3 to 18        carbon atoms and addition products thereof with 1 to 30 mol        ethylene oxide;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol according to DE 1165574 PS and/or mixed esters of        fatty acids containing 6 to 22 carbon atoms, methyl glucose and        polyols, preferably glycerol or polyglycerol,    -   mono-, di- and trialkyl phosphates and mono-, di- and/or        tri-PEG-alkyl phosphates and salts thereof,    -   wool wax alcohols,    -   polysiloxane/polyalkyl/polyether copolymers and corresponding        derivatives,    -   block copolymers, for example Polyethylene Glycol-30        Dipolyhydroxystearate;    -   polymer emulsifiers, for example Pemulen types (TR-1, TR-2) from        Goodrich;    -   polyalkylene glycols and    -   glycerol carbonate.

The addition products of ethylene oxide and/or propylene oxide ontofatty alcohols, fatty acids, alkylphenols or castor oil are knowncommercially available products. They are homolog mixtures of which theaverage degree of alkoxylation corresponds to the ratio between thequantities of ethylene oxide and/or propylene oxide and substrate withwhich the addition reaction is carried out. C₁₂₋₁₈ fatty acid monoestersand diesters of addition products of ethylene oxide onto glycerol areknown as refatting agents for cosmetic formulations from DE 2024051 PS.

Alkyl and alkenyl oligoglycosides, their production and their use areknown from the prior art. They are produced in particular by reactingglucose or oligosaccharides with primary C₈₋₁₈ alcohols. So far as theglycoside unit is concerned, both monoglycosides where a cyclic sugarunit is attached to the fatty alcohol by a glycoside bond and oligomericglycosides with a degree of oligomerization of preferably up to about 8are suitable. The degree of oligomerization is a statistical mean valueto which the homolog distribution typical of such technical productscorresponds.

Typical examples of suitable partial glycerides are hydroxystearic acidmonoglyceride, hydroxystearic acid diglyceride, isostearic acidmonoglyceride, isostearic acid diglyceride, oleic acid monoglyceride,oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic aciddiglyceride, linoleic acid monoglyceride, linoleic acid diglyceride,linolenic acid monoglyceride, linolenic acid diglyceride, erucic acidmonoglyceride, erucic acid diglyceride, tartaric acid monoglyceride,tartaric acid diglyceride, citric acid monoglyceride, citric aciddiglyceride, malic acid monoglyceride, malic acid diglyceride andtechnical mixtures thereof which may still contain small quantities oftriglyceride from the production process. Addition products of 1 to 30and preferably 5 to 10 mol ethylene oxide onto the partial glyceridesmentioned are also suitable.

Suitable sorbitan esters are sorbitan monoisostearate, sorbitansesquiisostearate, sorbitan diisostearate, sorbitan triisostearate,sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitantrioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitandierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate,sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitandihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate,sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate,sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate,sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof.Addition products of 1 to 30 and preferably 5 to 10 moles of ethyleneoxide onto the sorbitan esters mentioned are also suitable.

Typical examples of suitable polyglycerol esters are Polyglyceryl-2Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate(Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34),Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate(Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450),Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate(Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane®NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and PolyglycerylPolyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate andmixtures thereof. Examples of other suitable polyolesters are the mono-,di- and triesters of trimethylol propane or pentaerythritol with lauricacid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid,oleic acid, behenic acid and the like optionally reacted with 1 to 30mol ethylene oxide.

Other suitable emulsifiers are zwitterionic surfactants. Zwitterionicsurfactants are surface-active compounds which contain at least onequaternary ammonium group and at least one carboxylate and one sulfonategroup in the molecule. Particularly suitable zwitterionic surfactantsare the so-called betaines, such as the N-alkyl-N,N-dimethyl ammoniumglycinates, for example cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH— or —SO₃H— group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.Finally, cationic surfactants are also suitable emulsifiers, those ofthe esterquat type, preferably methyl-quaternized difatty acidtriethanolamine ester salts, being particularly preferred.

Fats and Waxes

Typical examples of fats are glycerides, i.e. solid or liquid, vegetableor animal products which consist essentially of mixed glycerol esters ofhigher fatty acids. Suitable waxes are inter alia natural waxes such as,for example, candelilla wax, carnauba wax, Japan wax, espartograss wax,cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax,montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax),uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffinwaxes and microwaxes; chemically modified waxes (hard waxes) such as,for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxesand synthetic waxes such as, for example, polyalkylene waxes andpolyethylene glycol waxes. Besides the fats, other suitable additivesare fat-like substances, such as lecithins and phospholipids. Lecithinsare known among experts as glycerophospholipids which are formed fromfatty acids, glycerol, phosphoric acid and choline by esterification.Accordingly, lecithins are also frequently referred to by experts asphosphatidyl cholines (PCs) and correspond to the following generalformula:

where R typically represents linear aliphatic hydrocarbon radicalscontaining 15 to 17 carbon atoms and up to 4 cis-double bonds. Examplesof natural lecithins are the kephalins which are also known asphosphatidic acids and which are derivatives of1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast, phospholipidsare generally understood to be mono- and preferably diesters ofphosphoric acid with glycerol (glycerophosphates) which are normallyclassed as fats. Sphingosines and sphingolipids are also suitable.Pearlizing Waxes

Suitable pearlizing waxes are, for example, alkylene glycol esters,especially ethylene glycol distearate; fatty acid alkanolamides,especially coconuffatty acid diethanolamide; partial glycerides,especially stearic acid monoglyceride; esters of polybasic, optionallyhydroxysubstituted carboxylic acids with fatty alcohols containing 6 to22 carbon atoms, especially long-chain esters of tartaric acid; fattycompounds, such as for example fatty alcohols, fatty ketones, fattyaldehydes, fatty ethers and fatty carbonates which contain in all atleast 24 carbon atoms, especially laurone and distearylether; fattyacids, such as stearic acid, hydroxystearic acid or behenic acid, ringopening products of olefin epoxides containing 12 to 22 carbon atomswith fatty alcohols containing 12 to 22 carbon atoms and/or polyolscontaining 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixturesthereof.

Consistency Factors and Thickeners

The consistency factors mainly used are fatty alcohols or hydroxyfattyalcohols containing 12 to 22 and preferably 16 to 18 carbon atoms and inaddition partial glycerides, fatty acids or hydroxyfatty acids. Acombination of these substances with alkyl oligoglucosides and/or fattyacid N-methyl glucamides of the same chain length and/or polyglycerolpoly-12-hydroxystearates is preferably used. Suitable thickeners are,for example, Aerosil types (hydrophilic silicas), polysaccharides, moreespecially xanthan gum, guar-guar, agar-agar, alginates and tyloses,carboxymethyl cellulose and hydroxyethyl cellulose, also relatively highmolecular weight polyethylene glycol monoesters and diesters of fattyacids, polyacrylates (for example Carbopols® and Pemulens [Goodrich] orSynthalens® [Sigma]; Keltrols from Kelco; Sepigels from Seppic; Salcaresfrom Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol andpolyvinyl pyrrolidone, surfactants such as, for example, ethoxylatedfatty acid glycerides esters of fatty acids with polyols, for examplepentaerythritol or trimethylol propane, narrow-range fatty alcoholethoxylates or alkyl oligoglucosides and electrolytes, such as sodiumchloride and ammonium chloride.

Superfatting Agents

Superfatting agents may be selected from such substances as, forexample, lanolin and lecithin and also polyethoxylated or acylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the fatty acidalkanolamides also serving as foam stabilizers.

Stabilizers

Metal salts of fatty acids such as, for example, magnesium, aluminiumand/or zinc stearate or ricinoleate may be used as stabilizers.

Polymers

Suitable cationic polymers are, for example, cationic cellulosederivatives such as, for example, the quaternized hydroxyethyl celluloseobtainable from Amerchol under the name of Polymer JR 400®, cationicstarch, copolymers of diallyl ammonium salts and acrylamides,quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, forexample, Luviquat® (BASF), condensation products of polyglycols andamines, quaternized collagen polypeptides such as, for example,Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L, Grünau),quaternized wheat polypeptides, polyethyleneimine, cationic siliconepolymers such as, for example, Amodimethicone, copolymers of adipic acidand dimethylamino-hydroxypropyl diethylenetriamine (Cartaretine®,Sandoz), copolymers of acrylic acid with dimethyl diallyl ammoniumchloride (Merquat® 550, Chemviron), polyaminopolyamides as described,for example, in FR 2252840 A and crosslinked water-soluble polymersthereof, cationic chitin derivatives such as, for example, quaternizedchitosan, optionally in microcrystalline distribution, condensationproducts of dihaloalkyls, for example dibromobutane, withbis-dialkylamines, for example bis-dimethylamino-1,3-propane, cationicguar gum such as, for example, Jaguar®CBS, Jaguar®C-17, Jaguar®C-16 ofCelanese, quaternized ammonium salt polymers such as, for example,Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are,for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinylether/maleicanhydride copolymers and esters thereof, uncrosslinked andpolyol-crosslinked polyacrylic acids, acrylamidopropyl trimethylammoniumchloride/acrylate copolymers, octylacrylamide/methylmethacrylate/tert.-butylaminoethyl methacrylate/2-hydroxypropylmethacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinylacetate copolymers, vinyl pyrrolidone/dimethylaminoethylmethacrylate/vinyl caprolactam terpolymers and optionally derivatizedcellulose ethers and silicones. Other suitable polymers and thickenerscan be found in Cosmetics & Toiletries, Vol. 108, May 1993, pages 95 etseq.

Silicone Compounds

Suitable silicone compounds are, for example, dimethyl polysiloxanes,methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds which may be both liquid andresin-like at room temperature. Other suitable silicone compounds aresimethicones which are mixtures of dimethicones with an average chainlength of 200 to 300 dimethylsiloxane units and hydrogenated silicates.A detailed overview of suitable volatile silicones can be found in Toddet al. in Cosm. Toil. 91, 27 (1976).

UV Protection Factors and Antioxidants

UV protection factors in the context of the invention are, for example,organic substances (light filters) which are liquid or crystalline atroom temperature and which are capable of absorbing ultraviolet orinfrared radiation and of releasing the energy absorbed in the form oflonger-wave radiation, for example heat. UV-B filters can be oil-solubleor water-soluble. The following are examples of oil-soluble substances:

-   -   3-benzylidene camphor or 3-benzylidene norcamphor and        derivatives thereof, for example 3-(4-methylbenzylidene)-camphor        as described in EP 0693471 B1;    -   4-aminobenzoic acid derivatives, preferably        4-(dimethylamino)-benzoic acid-2-ethylhexyl ester,        4-(dimethylamino)-benzoic acid-2-octyl ester and        4-(dimethylamino)-benzoic acid amyl ester;    -   esters of cinnamic acid, preferably 4-methoxycinnamic        acid-2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester,        4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic        acid-2-ethylhexyl ester (Octocrylene);    -   esters of salicylic acid, preferably salicylic acid-2-ethylhexyl        ester, salicylic acid-4-isopropylbenzyl ester, salicylic acid        homomenthyl ester;    -   derivatives of benzophenone, preferably        2-hydroxy-4-methoxybenzophenone,        2-hydroxy-4-methoxy-4′-methylbenzophenone,        2,2′-dihydroxy-4-methoxybenzophenone;    -   esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic        acid di-2-ethylhexyl ester;    -   triazine derivatives such as, for example,        2,4,6-trianilino-(p-carbo-2′ethyl-1′-hexyloxy)-1,3,5-triazine        and Octyl Triazone as described in EP 0818450 A1 or Dioctyl        Butamido Triazone (Uvasorb® HEB);    -   propane-1,3-diones such as, for example,        1-(4-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione;    -   ketotricyclo(5.2.1.0)decane derivatives as described in EP        0694521 B1.

Suitable water-soluble substances are

-   -   2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline        earth metal, ammonium, alkylammonium, alkanolammonium and        glucammonium salts thereof;    -   sulfonic acid derivatives of benzophenones, preferably        2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts        thereof;    -   sulfonic acid derivatives of 3-benzylidene camphor such as, for        example, 4-(2-oxo-3-bornylidenemethyl)-benzene sulfonic acid and        2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and salts        thereof.

Typical UV-A filters are, in particular, derivatives of benzoyl methanesuch as, for example,1-(4′-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione,4-tert.butyl-4′-methoxydibenzoyl methane (Parsol® 1789) or1-phenyl-3-(4′-isopropylphenyl)-propane-1,3-dione and the eneaminecompounds described in DE 19712033 A1 (BASF). The UV-A and UV-B filtersmay of course also be used in the form of mixtures. Particularlyfavorable combinations consist of the derivatives of benzoylmethane, forexample 4-tert.-butyl-4′-methoxydibenzoyl methane (Parsol® 1789) and2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl ester (Octocrylene) incombination with esters of cinnamic acid, preferably 4-methoxycinnamicacid-2-ethylhexyl ester and/or 4-methoxycinnamic acid propyl esterand/or 4-methoxycinnamic acid isoamyl ester. These combinations areadvantageously combined with water-soluble filters such as, for example,2-phenylbenzimidazole-5-sufonic acid and alkali metal, alkaline earthmetal, ammonium, alkylammonium, alkanolammonium and glucammonium salts.

Besides the soluble substances mentioned, insoluble light-blockingpigments, i.e. finely dispersed metal oxides or salts, may also be usedfor this purpose. Examples of suitable metal oxides are, in particular,zinc oxide and titanium dioxide and also oxides of iron, zirconiumoxide, silicon, manganese, aluminium and cerium and mixtures thereof.Silicates (talcum), barium sulfate and zinc stearate may be used assalts. The oxides and salts are used in the form of the pigments forskin-care and skin-protecting emulsions and decorative cosmetics. Theparticles should have a mean diameter of less than 100 nm, preferablybetween 5 and 50 nm and more preferably between 15 and 30 nm. They maybe spherical in shape although ellipsoidal particles or othernon-spherical particles may also be used. The pigments may also besurface-treated, i.e. hydrophilicized or hydrophobicized. Typicalexamples are coated titanium dioxides, for example Titandioxid T 805(Degussa) and Eusolex® T2000 (Merck). Suitable hydrophobic coatingmaterials are, above all, silicones and, among these, especiallytrialkoxyoctylsilanes or simethicones. So-called micro- or nanopigmentsare preferably used in sun protection products. Micronized zinc oxide ispreferably used. Other suitable UV filters can be found in P. Finkel'sreview in SÖFW-Journal 122, 543 (1996) and in Parfümerie und Kosmetik 3(1999), pages 11 et seq.

Besides the two groups of primary sun protection factors mentionedabove, secondary sun protection factors of the antioxidant type may alsobe used. Secondary sun protection factors of the antioxidant typeinterrupt the photochemical reaction chain which is initiated when UVrays penetrate into the skin. Typical examples are amino acids (forexample glycine, histidine, tyrosine, tryptophane) and derivativesthereof, imidazoles (for example urocanic acid) and derivatives thereof,peptides, such as D,L-carnosine, D-carnosine, L-carnosine andderivatives thereof (for example anserine), carotinoids, carotenes (forexample α-carotene, β-carotene, lycopene) and derivatives thereof,chlorogenic acid and derivatives thereof, liponic acid and derivativesthereof (for example dihydroliponic acid), aurothioglucose,propylthiouracil and other thiols (for example thioredoxine,glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl,methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl,γ-linoleyl, cholesteryl and glyceryl esters thereof) and their salts,dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionicacid and derivatives thereof (esters, ethers, peptides, lipids,nucleotides, nucleosides and salts) and sulfoximine compounds (forexample butionine sulfoximines, homocysteine sulfoximine, butioninesulfones, penta-, hexa- and hepta-thionine sulfoximine) in very smallcompatible dosages (for example pmole to μmole/kg), also (metal)chelators (for example α-hydroxyfatty acids, palmitic acid, phytic acid,lactoferrine), α-hydroxy acids (for example citric acid, lactic acid,malic acid), humic acid, bile acid, bile extracts, bilirubin,biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acidsand derivatives thereof (for example γ-linolenic acid, linoleic acid,oleic acid), folic acid and derivatives thereof, ubiquinone andubiquinol and derivatives thereof, vitamin C and derivatives thereof(for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (for example vitamin E acetate),vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoateof benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid,nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid andderivatives thereof, mannose and derivatives thereof,Superoxid-Dismutase, zinc and derivatives thereof (for example ZnO,ZnSO₄), selenium and derivatives thereof (for example seleniummethionine), stilbenes and derivatives thereof (for example stilbeneoxide, trans-stilbene oxide) and derivatives of these active substancessuitable for the purposes of the invention (salts, esters, ethers,sugars, nucleotides, nucleosides, peptides and lipids).

Biogenic Agents

In the context of the invention, biogenic agents are, for example,tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid,retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, aminoacids, ceramides, pseudoceramides, essential oils, plant extracts andvitamin complexes.

Deodorants and Germ Inhibitors

Cosmetic deodorants counteract, mask or eliminate body odors. Body odorsare formed through the action of skin bacteria on apocrine perspirationwhich results in the formation of unpleasant-smelling degradationproducts. Accordingly, deodorants contain active principles which act asgerm inhibitors, enzyme inhibitors, odor absorbers or odor maskers.Basically, suitable germ inhibitors are any substances which act againstgram-positive bacteria such as, for example, 4-hydroxybenzoic acid andsalts and esters thereof,N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)urea,2,4,4′-trichloro-2′-hydroxydiphenylether (triclosan),4-chloro-3,5-dimethylphenol,2,2′-methylene-bis-(6-bromo-4-chlorophenol),3-methyl-4(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol,3-(4-chlorophenoxy)propane-1,2-diol, 3-iodo-2-propinyl butyl carbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialperfumes, thymol, thyme oil, eugenol, clove oil, menthol, mint oil,farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate,glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylicacid-N-alkylamides such as, for example, salicylic acid-n-octyl amide orsalicylic acid-n-decyl amide.

Suitable enzyme inhibitors are, for example, esterase inhibitors.Esterase inhibitors are preferably trialkyl citrates, such as trimethylcitrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and,in particular, triethyl citrate (Hydagen® CAT, Henkel KGaA,Dusseldorf/FRG). Esterase inhibitors inhibit enzyme activity and thusreduce odor formation. Other esterase inhibitors are sterol sulfates orphosphates such as, for example, lanosterol, cholesterol, campesterol,stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids andesters thereof, for example glutaric acid, glutaric acid monoethylester, glutaric acid diethyl ester, adipic acid, adipic acid monoethylester, adipic acid diethyl ester, malonic acid and malonic acid diethylester, hydroxycarboxylic acids and esters thereof, for example citricacid, malic acid, tartaric acid or tartaric acid diethyl ester, and zincglycinate.

Suitable odor absorbers are substances which are capable of absorbingand largely retaining the odor-forming compounds. They reduce thepartial pressure of the individual components and thus also reduce therate at which they spread. An important requirement in this regard isthat perfumes must remain unimpaired. Odor absorbers are not activeagainst bacteria. They contain, for example, a complex zinc salt ofricinoleic acid or special perfumes of largely neutral odor known to theexpert as “fixateurs” such as, for example, extracts of ladanum orstyrax or certain abietic acid derivatives as their principal component.Odor maskers are perfumes or perfume oils which, besides theirodor-masking function, impart their particular perfume note to thedeodorants. Suitable perfume oils are, for example, mixtures of naturaland synthetic fragrances. Natural fragrances include the extracts ofblossoms, stems and leaves, fruits, fruit peel, roots, woods, herbs andgrasses, needles and branches, resins and balsams. Animal raw materials,for example civet and beaver, may also be used. Typical syntheticperfume compounds are products of the ester, ether, aldehyde, ketone,alcohol and hydrocarbon type. Examples of perfume compounds of the estertype are benzyl acetate, p-tert.butyl cyclohexylacetate, linalylacetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.Ethers include, for example, benzyl ethyl ether while aldehydes include,for example, the linear alkanals containing 8 to 18 carbon atoms,citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde,hydroxy-citronellal, lilial and bourgeonal. Examples of suitable ketonesare the ionones and methyl cedryl ketone. Suitable alcohols are anethol,citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethylalcohol and terpineol. The hydrocarbons mainly include the terpenes andbalsams. However, it is preferred to use mixtures of different perfumecompounds which, together, produce an agreeable fragrance. Othersuitable perfume oils are essential oils of relatively low volatilitywhich are mostly used as aroma components. Examples are sage oil,camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil,lime-blossom oil, juniper berry oil, vetivert oil, olibanum oil,galbanum oil, ladanum oil and lavendin oil. The following are preferablyused either individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,ahexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

Antiperspirants reduce perspiration and thus counteract underarm wetnessand body odor by influencing the activity of the eccrine sweat glands.Aqueous or water-free antiperspirant formulations typically contain thefollowing ingredients:

-   astringent active principles,-   oil components,-   nonionic emulsifiers,-   co-emulsifiers,-   consistency factors,-   auxiliaries in the form of, for example, thickeners or complexing    agents and/or-   non-aqueous solvents such as, for example, ethanol, propylene glycol    and/or glycerol.

Suitable astringent active principles of antiperspirants are, above all,salts of aluminium, zirconium or zinc. Suitable antihydrotic agents ofthis type are, for example, aluminium chloride, aluminium chlorohydrate,aluminium dichlorohydrate, aluminium sesquichlorohydrate and complexcompounds thereof, for example with 1,2-propylene glycol, aluminiumhydroxyallantoinate, aluminium chloride tartrate, aluminium zirconiumtrichlorohydrate, aluminium zirconium tetrachlorohydrate, aluminiumzirconium pentachlorohydrate and complex compounds thereof, for examplewith amino acids, such as glycine. Oil-soluble and water-solubleauxiliaries typically encountered in antiperspirants may also be presentin relatively small amounts. Oil-soluble auxiliaries such as theseinclude, for example,

-   inflammation-inhibiting, skin-protecting or pleasant-smelling    essential oils,-   synthetic skin-protecting agents and/or-   oil-soluble perfume oils.

Typical water-soluble additives are, for example, preservatives,water-soluble perfumes, pH regulators, for example buffer mixtures,water-soluble thickeners, for example water-soluble natural or syntheticpolymers such as, for example, xanthan gum, hydroxyethyl cellulose,polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

Film Formers

Standard film formers are, for example, chitosan, microcrystallinechitosan, quaternized chitosan, polyvinyl pyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic acidseries, quaternary cellulose derivatives, collagen, hyaluronic acid andsalts thereof and similar compounds.

Antidandruff Agents

Suitable antidandruff agents are Pirocton Olamin(1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinonemonoethanolamine salt), Baypival® (Climbazole), Ketoconazol®(4-acetyl-1-{4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}-piperazine,ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfurpolyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate,sulfur tar distillate, salicylic acid (or in combination withhexachlorophene), undecylenic acid, monoethanolamide sulfosuccinate Nasalt, Lamepon® UD (protein/undecylenic acid condensate), zincpyrithione, aluminium pyrithione and magnesium pyrithione/dipyrithionemagnesium sulfate.

Swelling Agents

Suitable swelling agents for aqueous phases are montmorillonites, clayminerals, Pemulen and alkyl-modified Carbopol types (Goodrich). Othersuitable polymers and swelling agents can be found in R. Lochhead=sreview in Cosm. Toil. 108, 95 (1993).

Insect Repellents

Suitable insect repellents are N,N-diethyl-m-toluamide, pentane-1,2-diolor Ethyl Butylacetylaminopropionate.

Self-tanning Agents and Depiqmenting Agents

A suitable self-tanning agent is dihydroxyacetone. Suitable tyrosineinhibitors which prevent the formation of melanin and are used indepigmenting agents are, for example, arbutin, koji acid, coumaric acidand ascorbic acid (vitamin C).

Hydrotropes

In addition, hydrotropes, for example ethanol, isopropyl alcohol orpolyols, may be used to improve flow behavior. Suitable polyolspreferably contain 2 to 15 carbon atoms and at least two hydroxylgroups. The polyols may contain other functional groups, more especiallyamino groups, or may be modified with nitrogen. Typical examples are

-   glycerol;-   alkylene glycols such as, for example, ethylene glycol, diethylene    glycol, propylene glycol, butylene glycol, hexylene glycol and    polyethylene glycols with an average molecular weight of 100 to 1000    dalton;-   technical oligoglycerol mixtures with a degree of self-condensation    of 1.5 to 10 such as, for example, technical diglycerol mixtures    with a diglycerol content of 40 to 50% by weight;-   methylol compounds such as, in particular, trimethylol ethane,    trimethylol propane, trimethylol butane, pentaerythritol and    dipentaerythritol;-   lower alkyl glucosides, particularly those containing 1 to 8 carbon    atoms in the alkyl group, for example methyl and butyl glucoside;-   sugar alcohols containing 5 to 12 carbon atoms, for example sorbitol    or mannitol,-   sugars containing 5 to 12 carbon atoms, for example glucose or    sucrose;-   amino sugars, for example glucamine;-   dialcoholamines, such as diethanolamine or 2-aminopropane-1,3-diol.    Preservatives

Suitable preservatives are, for example, phenoxyethanol, formaldehydesolution, parabens, pentanediol or sorbic acid and the other classes ofcompounds listed in Appendix 6, Parts A and B of the Kosm tikverordnung(“Cosmetics Directive”).

Perfume Oils

Suitable perfume oils are mixtures of natural and synthetic perfumes.Natural perfumes include the extracts of blossoms (lily, lavender, rose,jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli,petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel(bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom,costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood,cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage,thyme), needles and branches (spruce, fir, pine, dwarf pine), resins andbalsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animalraw materials, for example civet and beaver, may also be used. Typicalsynthetic perfume compounds are products of the ester, ether, aldehyde,ketone, alcohol and hydrocarbon type. Examples of perfume compounds ofthe ester type are benzyl acetate, phenoxyethyl isobutyrate,p-tert.butyl cyclohexylacetate, linalyl acetate, dimethyl benzylcarbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzylformate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate,styrallyl propionate and benzyl salicylate. Ethers include, for example,benzyl ethyl ether while aldehydes include, for example, the linearalkanals containing 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,lilial and bourgeonal. Examples of suitable ketones are the ionones,α-isomethylionone and methyl cedryl ketone. Suitable alcohols areanethol, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol. The hydrocarbons mainly include theterpenes and balsams. However, it is preferred to use mixtures ofdifferent perfume compounds which, together, produce an agreeablefragrance. Other suitable perfume oils are essential oils of relativelylow volatility which are mostly used as aroma components. Examples aresage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leafoil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil,galbanum oil, ladanum oil and lavendin oil. The following are preferablyused either individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

Dyes

Suitable dyes are any of the substances suitable and approved forcosmetic purposes as listed, for example, in the publication“Kosmetische Färbemittel” of the Farbstoffkommission der DeutschenForschungs-gemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106.These dyes are normally used in concentrations of 0.001 to 0.1% byweight, based on the mixture as a whole.

The total percentage content of auxiliaries and additives may be from 1to 50% by weight and is preferably from 5 to 40% by weight, based on theparticular formulation. The preparations may be produced by standard hotor cold processes and are preferably produced by the phase inversiontemperature method.

EXAMPLES

The wax, the partial glycerides (b) and the various surfactants (a) weremixed in various ratios by weight and the particle fineness wasdetermined by determining the particle size distribution in μm and themean particle diameter in μm by laser diffraction (Mastersizer 2000; seeproduct specification of MALVERN INSTRUMENTS GmbH, Herrenberg, Germany).Viscosity was measured by the Brookfield method (23° C., spindle 5, 10r.p.m., mPas). The results are set out in Table 1.

TABLE 1 Cosmetic preparations (quantities in % by weight activesubstance, based on the final composition) Composition (INCI) 1 2 3 4 C1C2 C3 C4 Cutina ® AGS 25 25 25 25 25 25 25 25 Ethyleneglycol DistearatePlantacare 818 ® 9.1 9.1 9.1 9.1 9.1 9.1 9.1 9.1 Coca GlucosideDehyton ® K — — 2.7 — — 2.7 — — Cocoamidopropyl Betaine Monomuls ®90-O18 — 1.8 2.5 1.25 — — 0.45 — Glyceryl Oleate Monomuls ® 90-L12 2.5 —— — 0.9 0.9 — 2.5 Glyceryl Laurate Cutina ® GMS — — — 1.25 — — 0.45 —Glyceryl Stearate Texapon ® N70 — — — — — — — 2.7 Sodium lauryl ethersulfate + 2 EO Glycerin 5 5 5 5 5 5 5 5 Benzoic acid 0.5 0.5 0.5 0.5 0.50.5 0.5 0.5 Water to 100 Ratio by weight a:b 4:1 5:1 5:1 6:1 10:1 13:110:1 5:1 Viscosity 4000 3000 3500 4000 9000 3500 11000 16000 Particlesize distribution <15 μm 99.9 98 98 99.9 83 89 85 91 15–20 μm 0.1 2 20.1 8.1 7 9 5 >20 μm — — — — 8.8 4 6 4 Mean particle 9.5 8 6.5 5.6 19 1318 14 diameter

1. An emulsifier mixture for a wax-based opacifier comprising: (a) analkyl and/or alkenyl oligoglycoside; (b) a fatty acid partial glyceride;and (c) at least one betaine compound of formula (IV)

 wherein R⁸CO is an aliphatic acyl group having from 6 to 22 carbonatoms and 0 or 1 to 3 double bonds, m is a number from 1 to 3, R⁶ ishydrogen or an alkyl group having from 1 to 4 carbon atoms, R⁷ is analkyl group having from 1 to 4 carbon atoms, n is a number from 1 to 6and X is an alkali metal, alkaline earth metal or ammonium ion, with theproviso that the ratio by weight of (a) plus (c) to (b) is between 6:1and 1.5:1 and wherein the composition is free from anionic surfactants.2. The emulsifier mixture of claim 1 wherein the alkyl and/or alkenyloligoglycoside is a compound of the formula (I):R¹O-[G]_(p)  (I) wherein R¹ is an alkyl and/or alkenyl group having from4 to 22 carbon atoms, G is a sugar unit having from 5 or 6 carbon atomsand p is a number from 1 to
 10. 3. The emulsifier mixture of claim 1wherein the fatty acid partial glyceride is a compound of the formula(II):

wherein R²CO is a linear or branched, saturated and/or unsaturated acylgroup having from 6 to 22 carbon atoms, each of R³ and R⁴ isindependently the same as R²CO or OH, and wherein the sum (m+n+p) is 0or a number from 1 to 100, with the proviso that at least one of R³ andR⁴ is OH.
 4. The emulsifier mixture of claim 1 wherein the weight ratioof (a) plus (c) to (b) is from 2:1 to 3:1.
 5. An opacifier compositioncomprising: (1) a wax; (2) an emulsifier mixture comprising: (a) analkyl and/or alkenyl oligoglycoside; (b) a fatty acid partial glyceride;and (c) at least one betaine compound of formula (IV)

 wherein R⁸CO is an aliphatic acyl group having from 6 to 22 carbonatoms and 0 or 1 to 3 double bonds, m is a number from 1 to 3, R⁶ ishydrogen or an alkyl group having from 1 to 4 carbon atoms, R⁷ is analkyl group having from 1 to 4 carbon atoms, n is a number from 1 to 6and X is an alkali metak alkaline earth metal or ammonium ion, with theproviso that the ratio by weight of (a) plus (c) to (b) is between 6:1and 1.5:1, and wherein the composition is free from anionic surfactants.6. The composition of claim 5 wherein the alkyl and/or alkenyloligoglycoside is a compound of the formula (I):R¹O-[g]_(p)  (I) wherein R¹ is an alkyl and/or alkenyl group having from4 to 22 carbon atoms, G is a sugar unit having from 5 or 6 carbon atomsand p is a number from 1 to
 10. 7. The composition of claim 5 whereinthe fatty acid partial glyceride is a compound of the formula (II):

wherein R²CO is a linear or branched, saturated and/or unsaturated acylgroup having from 6 to 22 carbon atoms, each of R³ and R⁴ is OH orindependently the same as R²CO wherein the sum (m+n+p) is 0 or a numberfrom 1 to 100, with the proviso that at least one of R³ and R⁴ is OH. 8.The composition of claim 5 wherein the weight ratio of (a) plus (c) to(b) is from 2:1 to 3:1.
 9. The composition of claim 5 wherein the solidscontent is from 25 to 45% by weight, based on the final composition. 10.The composition of claim 5 wherein at least 90% of the composition hasparticle sizes below 10 μm.